CN106831845A - Boracic organo-silicon compound, Preparation Method And The Use - Google Patents
Boracic organo-silicon compound, Preparation Method And The Use Download PDFInfo
- Publication number
- CN106831845A CN106831845A CN201510888485.7A CN201510888485A CN106831845A CN 106831845 A CN106831845 A CN 106831845A CN 201510888485 A CN201510888485 A CN 201510888485A CN 106831845 A CN106831845 A CN 106831845A
- Authority
- CN
- China
- Prior art keywords
- boracic
- organo
- base
- silicon compound
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000000126 substance Substances 0.000 claims abstract description 30
- 239000004327 boric acid Substances 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 25
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 125000000392 cycloalkenyl group Chemical group 0.000 claims abstract description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 12
- -1 cyclopropanyl Chemical group 0.000 claims description 86
- 238000000034 method Methods 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 21
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 21
- 239000004913 cyclooctene Substances 0.000 claims description 21
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 claims description 20
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 18
- UCIYGNATMHQYCT-OWOJBTEDSA-N cyclodecene Chemical compound C1CCCC\C=C\CCC1 UCIYGNATMHQYCT-OWOJBTEDSA-N 0.000 claims description 14
- 150000001721 carbon Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 42
- 239000000178 monomer Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 125000003342 alkenyl group Chemical group 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 8
- 238000010183 spectrum analysis Methods 0.000 description 7
- 239000005052 trichlorosilane Substances 0.000 description 7
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 7
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 6
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000001642 boronic acid derivatives Chemical group 0.000 description 5
- AUNNTHNQWVSPPP-UHFFFAOYSA-N cyclopropyloxyboronic acid Chemical class OB(O)OC1CC1 AUNNTHNQWVSPPP-UHFFFAOYSA-N 0.000 description 5
- NVYQDQZEMGUESH-UHFFFAOYSA-N dimethylsilyloxy(dimethyl)silane Chemical class C[SiH](C)O[SiH](C)C NVYQDQZEMGUESH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 5
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 125000001118 alkylidene group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- GTYLWUZKRJYAJZ-UHFFFAOYSA-N dibutoxyborinic acid Chemical compound CCCCOB(O)OCCCC GTYLWUZKRJYAJZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910020388 SiO1/2 Inorganic materials 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- OWKFISCJXZGUGH-UHFFFAOYSA-N cyclopenten-1-yloxyboronic acid Chemical compound OB(O)OC1=CCCC1 OWKFISCJXZGUGH-UHFFFAOYSA-N 0.000 description 3
- XXUFLAUHHBETOY-UHFFFAOYSA-N di(propan-2-yloxy)borinic acid Chemical compound CC(C)OB(O)OC(C)C XXUFLAUHHBETOY-UHFFFAOYSA-N 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910020485 SiO4/2 Inorganic materials 0.000 description 2
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 2
- XZWQKJXJNKYMAP-UHFFFAOYSA-N cyclohexen-1-ylboronic acid Chemical class OB(O)C1=CCCCC1 XZWQKJXJNKYMAP-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- VLSJPRHEVMZIII-UHFFFAOYSA-N diethoxyborinic acid Chemical compound CCOB(O)OCC VLSJPRHEVMZIII-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229930006728 pinane Natural products 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical class C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- ZOAMZFNAPHWBEN-UHFFFAOYSA-N 2-$l^{1}-oxidanylpropane Chemical compound CC(C)[O] ZOAMZFNAPHWBEN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YJAOLKPFNRIPMM-UHFFFAOYSA-N B(O)(O)O.C1(=CCCC1)CC(O)(C)C(C)(C)O Chemical compound B(O)(O)O.C1(=CCCC1)CC(O)(C)C(C)(C)O YJAOLKPFNRIPMM-UHFFFAOYSA-N 0.000 description 1
- HHSBVDMNYYWPIZ-UHFFFAOYSA-N B(O)(O)O.C1(CC1)CC(O)(C)C(C)(C)O Chemical compound B(O)(O)O.C1(CC1)CC(O)(C)C(C)(C)O HHSBVDMNYYWPIZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MCZQGJXPPZHLTG-UHFFFAOYSA-N C.[Cl] Chemical compound C.[Cl] MCZQGJXPPZHLTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910020447 SiO2/2 Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- IIIRWTKKXFPPSK-UHFFFAOYSA-N [diacetyloxy(cyclodecyl)silyl] acetate Chemical compound C1(CCCCCCCCC1)[Si](OC(C)=O)(OC(C)=O)OC(C)=O IIIRWTKKXFPPSK-UHFFFAOYSA-N 0.000 description 1
- FKRDHUIMAFRHIV-UHFFFAOYSA-N [diacetyloxy(cyclopenten-1-yl)silyl] acetate Chemical compound C1(=CCCC1)[Si](OC(C)=O)(OC(C)=O)OC(C)=O FKRDHUIMAFRHIV-UHFFFAOYSA-N 0.000 description 1
- FIXBYOMYXWBMCL-UHFFFAOYSA-N [diacetyloxy(cyclopropyl)silyl] acetate Chemical compound C1(CC1)[Si](OC(C)=O)(OC(C)=O)OC(C)=O FIXBYOMYXWBMCL-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- TWOWMEIVGWYKOW-UHFFFAOYSA-N boric acid cyclohexene Chemical compound B(O)(O)O.C1=CCCCC1 TWOWMEIVGWYKOW-UHFFFAOYSA-N 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KZBRQBLVIXFBRM-UHFFFAOYSA-N cyclodecyl(hydroxy)silane Chemical compound C1(CCCCCCCCC1)[SiH2]O KZBRQBLVIXFBRM-UHFFFAOYSA-N 0.000 description 1
- GALXJLVCXJFVKS-UHFFFAOYSA-N cyclohepten-1-yl(hydroxy)silane Chemical compound C1(=CCCCCC1)[SiH2]O GALXJLVCXJFVKS-UHFFFAOYSA-N 0.000 description 1
- XNJZRLPHSWXMGX-UHFFFAOYSA-N cyclohepten-1-yl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1=CCCCCC1 XNJZRLPHSWXMGX-UHFFFAOYSA-N 0.000 description 1
- WZKDOYCHDDFFDS-UHFFFAOYSA-N cyclohepten-1-yl(trimethoxy)silane Chemical compound C1(=CCCCCC1)[Si](OC)(OC)OC WZKDOYCHDDFFDS-UHFFFAOYSA-N 0.000 description 1
- SVCIYLVBBUPLPQ-UHFFFAOYSA-N cyclopenten-1-yl(hydroxy)silane Chemical compound C1(=CCCC1)[SiH2]O SVCIYLVBBUPLPQ-UHFFFAOYSA-N 0.000 description 1
- IMFMUWJYTDUSIU-UHFFFAOYSA-N cyclopenten-1-yl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1=CCCC1 IMFMUWJYTDUSIU-UHFFFAOYSA-N 0.000 description 1
- VZNFEFZDFPUTFJ-UHFFFAOYSA-N cyclopenten-1-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1=CCCC1 VZNFEFZDFPUTFJ-UHFFFAOYSA-N 0.000 description 1
- XGIYFVGVVNIXQX-UHFFFAOYSA-N cyclopropyl(hydroxy)silane Chemical compound O[SiH2]C1CC1 XGIYFVGVVNIXQX-UHFFFAOYSA-N 0.000 description 1
- PROCFPHHUVOPIT-UHFFFAOYSA-N cyclopropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CC1 PROCFPHHUVOPIT-UHFFFAOYSA-N 0.000 description 1
- FWCBQAXNMWDAFK-UHFFFAOYSA-N cyclopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CC1 FWCBQAXNMWDAFK-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AEWZJOYODGXOOB-UHFFFAOYSA-N hex-1-enyl(hydroxy)silane Chemical compound CCCCC=C[SiH2]O AEWZJOYODGXOOB-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical group OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- OWVRZZUCDKQKGW-UHFFFAOYSA-N trichloro(cyclodecyl)silane Chemical compound C1(CCCCCCCCC1)[Si](Cl)(Cl)Cl OWVRZZUCDKQKGW-UHFFFAOYSA-N 0.000 description 1
- YFYGSQVZSRGNGZ-UHFFFAOYSA-N trichloro(cyclohepten-1-yl)silane Chemical compound C1(=CCCCCC1)[Si](Cl)(Cl)Cl YFYGSQVZSRGNGZ-UHFFFAOYSA-N 0.000 description 1
- ABADXEJAOMPRBW-UHFFFAOYSA-N trichloro(cyclopenten-1-yl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CCCC1 ABADXEJAOMPRBW-UHFFFAOYSA-N 0.000 description 1
- QDMNTBBQSKPIMC-UHFFFAOYSA-N trichloro(cyclopropyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CC1 QDMNTBBQSKPIMC-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
- C07F7/0879—Hydrosilylation reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention provides boracic organo-silicon compound, Preparation Method And The Use.Its molecular skeleton of boracic organo-silicon compound of the present invention is made up of cycloalkenyl group, silicon oxygen bond (Si O) and cycloalkyl, and contains three boric acid or borate group being bonded via cycloalkyl.Boracic organo-silicon compound of the present invention are used as the tackifier of addition curable organopolysiloxane composition, can be in hot and humid and UV environment for its solidfied material provides cohesive stable sufficiently and for a long time.Additionally, the present invention prepares boracic organo-silicon compound by silicon hydrogenation, it is obtained in that chemical constitution is controllable, there is no the boracic organo-silicon compound of accessory substance, quality and stable performance.
Description
Technical field
The present invention relates to boracic organo-silicon compound, more particularly to carried out containing cycloalkenyl group and via cycloalkyl
The boric acid of bonding or the boracic organo-silicon compound of borate group, and the boracic organo-silicon compound
The purposes of preparation method and the tackifier as addition curable organopolysiloxane composition.
Background technology
Addition curable organopolysiloxane composition is because its solidification process no coupling product, shrinkage factor are small, energy
The advantages of deep cure, obtain extensively should in fields such as large scale integrated circuit, LED, solar cells
With.However, because its solidfied material contains substantial amounts of nonpolar organic group, molecular surface energy is low, thus
Cohesive to base materials such as glass, resins is very poor.Therefore, the organic poly- silica of addition curable how is improved
Alkane composition solidfied material, to the cohesive of base material, is always the study hotspot in the field.
Tackifier are added in addition curable organopolysiloxane composition, is to improve its solidfied material to base
One of effective means of material cohesive.At present, a large amount of available tackifier are had been disclosed for.In these increasings
In stick, organic silicon tackifier are same or like because of its chemical constitution and polysiloxanes, and the two has good
Good compatibility, thus be used widely.
CN102892837A, CN103154144A, CN104395406A, CN104870568A point
Do not disclose as the ring-type or linear oligosaccharides siloxanes of tackifier, it has tri-alkoxy siloxy and first
Base hydrogen siloxy.CN102276989A is disclosed as the cyclic oligomer siloxanes of tackifier, and it contains
Epoxy radicals and methyl hydrogen siloxy.These tackifier are containing the alkoxy or epoxy as tackifying group
While base, also containing the si-h bond (Si-H) that can provide hydrosilylation reactions activity, due to silicon
Hydrogen bond is also easy to produce hydrogen during storing, and causes the use of these tackifier to there is potential safety hazard.
CN102892837A, JP2010248410A are individually disclosed with isocyanuric acid ester group, allyl
The tackifier of base and epoxy radicals and/or alkoxysilyl.These tackifier replace silicon hydrogen with pi-allyl
Key can avoid the safety triggered because si-h bond is also easy to produce hydrogen to provide hydrosilylation reactions activity
Nitrogen-atoms in problem, but isocyanuric acid ester group is easily caused platinum group catalyst poisoning, so as to limit it
Use in addition curable organopolysiloxane composition.
JP2012149131A, CN101443400A, CN102732040A, CN102977604A point
Do not disclose the organopolysiloxane tackifier containing alkenyl, phenyl, epoxy radicals and alkoxy, its be by
Alkoxy silane monomer containing alkenyl, the alkoxy silane monomer containing phenyl, the alkoxyl silicone containing epoxy radicals
Alkane monomer is made through condensation reaction.These tackifier do not contain nitrogen-atoms, in can avoiding the occurrence of catalyst
The problem of poison, but its preparation uses condensation reaction technique, and used the trifunctional alkane of larger proportion
TMOS monomer, causes its chemical constitution to be difficult to be effectively controlled, and there is more accessory substance, from
And have impact on the quality and performance of its product.
CN103739848A, CN103589164A are individually disclosed as the boracic perester radical of tackifier
Organic polyborosiloxane of group, borate group therein is respectively anti-through condensation by boric acid or the ester of boric acid three
Should be formed, and boron atom is only bonded to polymer chain by boron oxygen key (B-O).Based on aforementioned
Reason, these organic polyborosiloxanes equally exist chemical constitution and are difficult to effectively control, and are waited accessory substance more and lacked
Point.It is additionally, since boron oxygen key chance water or moisture is easily hydrolyzed, on organic polyborosiloxane molecule
Easily hydrolysis comes off borate group, it is impossible to provide stable viscous sufficiently and for a long time in hot and humid environment
Conjunction property.
JP2000169482A discloses the organo-silicon compound as the phenolic hydroxy group of tackifier, its be by
Organo-silicon compound containing alkenyl and si-h bond (Si-H) carry out silicon hydrogen with the phenol compound containing alkenyl
Change reaction (hydrosilylation) to be made.Because phenolic hydroxyl group has stronger suction to ultraviolet (UV)
Adduction, the UV resistance of the organo-silicon compound is unsatisfactory, thus when as addition curable
During the tackifier of organopolysiloxane, the organo-silicon compound cannot be in UV environment for it solidifies
Thing provides cohesive stable sufficiently and for a long time, therefore the tackifier are not suitable for needing for a long time exposed to purple
The application field of outer thread environment, such as solar cell.
Therefore, one kind is badly in need of at present can be in hot and humid and UV environment for addition curable is organic
Polysiloxane composition provides the organic silicon tackifier of cohesive stable sufficiently and for a long time.
The content of the invention
Problems to be solved by the invention
It is an object of the invention to provide boracic organo-silicon compound, it is used as the organic poly- silicon of addition curable
The tackifier of silicone compositions, can be in hot and humid and UV environment for its solidfied material is provided fully
And cohesive steady in a long-term.Another object of the present invention is to provide the boracic organo-silicon compound
Preparation method, it is obtained in that chemical constitution is controllable, there is no accessory substance, quality and stable performance
Boracic organo-silicon compound.It is still another object of the present invention to provide the boracic organo-silicon compound
Purposes, its tackifier for being used as addition curable organopolysiloxane composition.
The scheme for solving problem
To realize above-mentioned purpose of the invention, the present invention provides boracic organo-silicon compound, and it has formula (I)
Shown chemical constitution：
In formula (I)：
B is boron atom,
Q is the cycloalkenyl group of substituted or unsubstituted carbon number 3-20,
L is the cycloalkyl of substituted or unsubstituted carbon number 3-20,
Two OR being connected with B1In two R1The respectively alkyl of hydrogen atom or carbon number 1-20,
Or, two OR being connected with B1In two R1It is interconnected to form the alkylene of carbon number 2-20
Base.
According to boracic organo-silicon compound of the present invention, it is preferable that the Q is selected from substitution or does not take
The cyclopropanyl in generation, cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclo-octene base, cyclonoene base, ring
Decene base, cyclododecene base or norbornene.
According to boracic organo-silicon compound of the present invention, it is preferable that the Q is selected from substitution or does not take
The cyclohexenyl group or norbornene in generation.
According to boracic organo-silicon compound of the present invention, it is preferable that the L is selected from substitution or does not take
The cyclopropyl in generation, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, ring 12
Alkyl or norborneol alkyl.
According to boracic organo-silicon compound of the present invention, it is preferable that the L is selected from substitution or does not take
The cyclohexyl in generation.
The present invention also provides the method for preparing above-mentioned boracic organo-silicon compound, including：Send out following material
Raw silicon hydrogenation：
Silicone compounds shown in (a) formula (II)：
In formula (II), Q is identical with defined in formula (I),
Boric acid or boric acid ester compound shown in (b) formula (III)：
In formula (III)：
L ' is selected from the cycloalkenyl group of substituted or unsubstituted carbon number 3-20,
R1It is identical with defined in formula (I).
According to method of the present invention, it is preferable that the L ' be selected from substituted or unsubstituted cyclopropanyl,
Cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclo-octene base, cyclonoene base, cyclodecene base, ring 12
Alkenyl or norbornene.
According to method of the present invention, it is preferable that the L ' is selected from substituted or unsubstituted cyclohexenyl group.
The present invention also provides above-mentioned boracic organo-silicon compound or organic by the boracic of above method preparation
The purposes of silicon compound, its tackifier for being used as addition curable organopolysiloxane composition.
The effect of invention
Boracic organo-silicon compound of the present invention, its molecular skeleton is by cycloalkenyl group, silicon oxygen bond (Si-O)
Constituted with cycloalkyl, and contain three boric acid or borate group being bonded via cycloalkyl.According to
Boracic organo-silicon compound of the present invention, it is used as addition curable organopolysiloxane composition
Tackifier, can be in hot and humid and UV environment for its solidfied material provides what is stablized sufficiently and for a long time
Cohesive.Additionally, the present invention prepares boracic organo-silicon compound by silicon hydrogenation, with condensation reaction
Technique is compared, and method of the present invention is obtained in that chemical constitution is controllable, there is no accessory substance,
Quality and the boracic organo-silicon compound of stable performance.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention
It is not limited to this.
Heretofore described " substitution " refers to be taken described in the substituted base of hydrogen atom in group or compound
Generation.Wherein, it is described substitution base include but is not limited to alkyl, aryl, alkenyl, alkynyl, halogen atom,
Alkoxy, hydroxyl, epoxy radicals, amido, sulfydryl, nitro, carboxylic acid group, sulfonic group, ester group, acid amides
Base or heterocyclic radical.
Heretofore described " halogen atom " refers to fluorine atom, chlorine atom, bromine atoms or iodine atom.
Heretofore described " viscosity ", in case of no particular description, each means at 23 DEG C
By the dynamic viscosity of rotary viscosity design determining, unit is mPas.
Heretofore described " Vi " represents vinyl, and described " Me " represents methyl.
<Boracic organo-silicon compound>
Boracic organo-silicon compound of the present invention, its molecular skeleton is by cycloalkenyl group, silicon oxygen bond (Si-O)
Constituted with cycloalkyl, and contain three boric acid or borate group being bonded via cycloalkyl.This hair
Bright described boracic organo-silicon compound are used as the tackifier of addition curable organopolysiloxane composition,
Can be in hot and humid and UV environment for its solidfied material provides cohesive stable sufficiently and for a long time.
Boracic organo-silicon compound of the present invention, it has the chemical constitution shown in formula (I)：
In formula (I)：
B is boron atom,
Q is the cycloalkenyl group of substituted or unsubstituted carbon number 3-20,
L is the cycloalkyl of substituted or unsubstituted carbon number 3-20,
Two OR being connected with B1In two R1The respectively alkyl of hydrogen atom or carbon number 1-20,
Or, two OR being connected with B1In two R1It is interconnected to form the alkylene of carbon number 2-20
Base.
In formula (I), the Q is preferably the cycloalkenyl group of carbon number 4-15, more preferably carbon number
The cycloalkenyl group of 5-8.
The example of the Q includes but is not limited to substituted or unsubstituted cyclopropanyl, cyclobutane base, ring penta
Alkenyl, cyclohexenyl group, cyclo-octene base, cyclonoene base, cyclodecene base, cyclododecene base or ENB
Base.According to the preferred embodiment of the present invention, the Q is selected from substituted or unsubstituted cyclohexenyl group or drop
Borneol alkenyl.
In formula (I), the L is preferably the cycloalkyl of carbon number 4-15, more preferably carbon number
The cycloalkyl of 5-8.
The example of the L include but is not limited to substituted or unsubstituted cyclopropyl, cyclobutyl, cyclopenta,
Cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, cyclo-dodecyl or norborneol alkyl.According to the present invention
Preferred embodiment, the L is selected from substituted or unsubstituted cyclohexyl.
In formula (I), as the R1During for alkyl, its alkyl for being preferably carbon number 1-10 is more excellent
Elect the alkyl of carbon number 1-4 as.
The R1Example during for alkyl include but is not limited to methyl, ethyl, propyl group, butyl, amyl group,
Hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl or its isomers.Preferably,
The R1It is methyl, ethyl, propyl group, butyl or its isomers.
In formula (I), as the R1During for alkylidene, its alkylidene for being preferably carbon number 2-15,
The more preferably alkylidene of carbon number 2-10.
The R1Example during for alkylidene includes but is not limited to ethylidene, propylidene, butylidene, Asia
Amyl group, hexylidene, heptamethylene, octamethylene, nonylene, decylene, alkylene undecyl, sub- dodecane
Base, sub- pinane base or its isomers.Preferably, the R1It is ethylidene, propylidene, 2,3- dimethyl
Butylidene or sub- pinane base.
In the present invention, the boracic organo-silicon compound preferably have following formula (I-1) to formula (I-16)
Shown chemical constitution：
According to the preferred embodiment of the present invention, boracic organo-silicon compound of the present invention have above-mentioned
Chemical constitution shown in formula (I-7) or formula (I-15).
<The method for preparing boracic organo-silicon compound>
The present invention prepares the boracic organo-silicon compound by silicon hydrogenation.Using of the present invention
Method, is obtained in that chemical constitution is controllable, there is no the boracic of accessory substance, quality and stable performance
Organo-silicon compound.
Method of the present invention, including：Make following material that silicon hydrogenation to occur：
Silicone compounds shown in (a) formula (II)：
In formula (II), Q is identical with defined in formula (I),
Boric acid or boric acid ester compound shown in (b) formula (III)：
In formula (III)：
L ' is selected from the cycloalkenyl group of substituted or unsubstituted carbon number 3-20,
R1It is identical with defined in formula (I).
In formula (III), the L ' is preferably the cycloalkenyl group of carbon number 4-15, more preferably carbon atom
The cycloalkenyl group of number 5-8.
The example of the L ' includes but is not limited to substituted or unsubstituted cyclopropanyl, cyclobutane base, ring penta
Alkenyl, cyclohexenyl group, cyclo-octene base, cyclonoene base, cyclodecene base, cyclododecene base or ENB
Base.According to the preferred embodiment of the present invention, the L ' is selected from substituted or unsubstituted cyclohexenyl group.
In method of the present invention, the silicone compounds (a) are by following monomer (a1)
It is made through hydrolysis-condensation reaction with monomer (a2)：
(a1)：Trifunctional monomer shown in formula (IV)：
QSi(R2)3 (IV)
In formula (IV), Q and identical, the R defined in formula (I)2It is hydroxyl or hydrolyzable
Group；
(a2)：Monofunctional monomer or 1,1,3,3- tetramethyl disiloxanes shown in formula (V)：
H(CH3)2SiR2 (V)
In formula (V), R2It is identical with defined in formula (IV).
In formula (IV) and formula (V), the example of the hydrolyzable groups include but is not limited to halogen atom,
The alkoxy of carbon number 1-10 or the acyloxy of carbon number 2-10.Preferably, the hydrolyzable base
Group is selected from chlorine atom, methoxyl group, ethyoxyl, isopropoxy or acetoxyl group.
The example of the monomer (a1) is included but is not limited to：
Ortho-siliformic acid monomer, such as cyclopropanyl silanol, cyclobutane base silanol, cyclopentenyl silanol, ring
Hexenyl silanol, cycloheptenyl silanol, cyclo-octene base silanol, cyclonoene base silanol, cyclodecyl silanol,
Cyclododecene base silanol or norbornene silanol；
Trihalosilane monomer, such as cyclopropanyl trichlorosilane, cyclobutane base trichlorosilane, cyclopentenyl
Trichlorosilane, cyclohexenyl group trichlorosilane, cycloheptenyl trichlorosilane, cyclo-octene base trichlorosilane, ring
Nonene base trichlorosilane, cyclodecyl trichlorosilane, cyclododecene base trichlorosilane or norbornene trichlorine
Silane；
Trialkoxy silane monomer, such as cyclopropanyl trimethoxy silane, cyclopropanyl triethoxysilane,
The isopropoxy silane of cyclopropanyl three, cyclobutane base trimethoxy silane, cyclobutane base triethoxysilane,
The isopropoxy silane of cyclobutane base three, cyclopentenyl trimethoxy silane, cyclopentenyl triethoxysilane,
The isopropoxy silane of cyclopentenyl three, cyclohexenyl group trimethoxy silane, cyclohexenyl group triethoxysilane,
The isopropoxy silane of cyclohexenyl group three, cycloheptenyl trimethoxy silane, cycloheptenyl triethoxysilane,
The isopropoxy silane of cycloheptenyl three, cyclo-octene base trimethoxy silane, cyclo-octene base triethoxysilane,
The isopropoxy silane of cyclo-octene base three, cyclonoene base trimethoxy silane, cyclonoene ethyl triethoxy silicane alkane,
The isopropoxy silane of cyclonoene base three, cyclodecene base trimethoxy silane, cyclodecene ethyl triethoxy silicane alkane,
The isopropoxy silane of cyclodecene base three, cyclododecene base trimethoxy silane, cyclododecene base triethoxy
Silane, the isopropoxy silane of cyclododecene base three, norbornene trimethoxy silane, norbornene
Triethoxysilane or the isopropoxy silane of norbornene three；
Three acyloxy silane monomers, such as cyclopropanyl triacetoxysilane, cyclobutane base triacetoxyl group
Silane, cyclopentenyl triacetoxysilane, cyclohexenyl group triacetoxysilane, the second of cycloheptenyl three
Acyloxy silane, cyclo-octene base triacetoxysilane, cyclonoene base triacetoxysilane, cyclodecyl
Triacetoxysilane, cyclododecene base triacetoxysilane or norbornene triacetoxyl group silicon
Alkane.
Preferably, the monomer (a1) be selected from cyclohexenyl group trichlorosilane, ENB base trichlorosilane,
Cyclohexenyl group trimethoxy silane, cyclohexenyl group triethoxysilane, the isopropoxy silane of cyclohexenyl group three,
Norbornene trimethoxy silane, norbornene triethoxysilane, the isopropyl oxygen of norbornene three
Base silane, cyclohexenyl group triacetoxysilane or norbornene triacetoxysilane.
The example of the monomer (a2) is included but is not limited to：Dimethyl methoxy silane, dimethylethoxy
Base silane, dimethylchlorosilane or 1,1,3,3- tetramethyl disiloxanes.Preferably, the monomer (a2)
It is 1,1,3,3- tetramethyl disiloxanes.
By the monomer (a1) siliconization is prepared with the monomer (a2) through hydrolysis-condensation reaction
The technique of compound (a) has no particular limits, and can use hydrolytic condensation technique well known in the art.Example
Such as, can be using the correlation as disclosed in JP2000169482A, EP1055674A1, US5614640A
Technique.
According to the preferred embodiment of the present invention, the silicone compounds (a) have formula (II-1) or
Chemical constitution shown in formula (II-2)：
In method of the present invention, the example of the boric acid or boric acid ester compound (b) include but
It is not limited to：
Substituted or unsubstituted cyclenes ylboronic acid, such as substituted or unsubstituted cyclopropanyl boric acid, cyclobutane
Ylboronic acid, cyclopentenyl boric acid, cyclohexenyl group boric acid, cyclo-octene base boric acid, cyclonoene ylboronic acid, ring
Decene ylboronic acid, cyclododecene ylboronic acid or ENB ylboronic acid；
Substituted or unsubstituted cyclenes ylboronic acid dialkyl ester, such as substituted or unsubstituted cyclopropanyl boric acid
Dimethyl ester, cyclopropanyl boric acid diethylester, cyclopropanyl boric acid diisopropyl ester, the fourth of cyclopropanyl boric acid two
Ester, cyclobutane base trimethyl borate, cyclobutane base boric acid diethylester, cyclobutane base boric acid diisopropyl ester,
Cyclobutane base boric acid dibutyl ester, cyclopentenyl trimethyl borate, cyclopentenyl boric acid diethylester, cyclopentene
Ylboronic acid diisopropyl ester, cyclopentenyl boric acid dibutyl ester, cyclohexenyl group trimethyl borate, cyclohexenyl group boron
Diethyl phthalate, cyclohexenyl group boric acid diisopropyl ester, cyclohexenyl group boric acid dibutyl ester, cyclo-octene base boric acid two
Methyl esters, cyclo-octene base boric acid diethylester, cyclo-octene base boric acid diisopropyl ester, cyclo-octene base boric acid dibutyl ester,
Cyclonoene ylboronic acid dimethyl ester, cyclonoene ylboronic acid diethylester, cyclonoene ylboronic acid diisopropyl ester, ring nonyl
Ene boric acid dibutyl ester, cyclodecene ylboronic acid dimethyl ester, cyclodecene ylboronic acid diethylester, cyclodecene base boron
Sour diisopropyl ester, cyclodecene ylboronic acid dibutyl ester, cyclododecene ylboronic acid dimethyl ester, cyclododecene base boron
Diethyl phthalate, cyclododecene ylboronic acid diisopropyl ester, cyclododecene ylboronic acid dibutyl ester, norbornene
Trimethyl borate, ENB ylboronic acid diethylester, ENB ylboronic acid diisopropyl ester or ENB
Ylboronic acid dibutyl ester；
Substituted or unsubstituted cyclenes ylboronic acid alkylidene diester, such as cyclopropanyl boronicacid ethylene glycol ester, ring
Propylene ylboronic acid propylene glycol ester, cyclopropanyl pinacol borate, cyclopropanyl boric acid pinane diol ester,
Cyclobutane base boronicacid ethylene glycol ester, cyclobutane base boric acid propylene glycol ester, cyclobutane base pinacol borate,
Cyclobutane base boric acid pinane diol ester, cyclopentenyl boronicacid ethylene glycol ester, cyclopentenyl boric acid propylene glycol ester,
Cyclopentenyl pinacol borate, cyclopentenyl boric acid pinane diol ester, cyclohexenyl group boronicacid ethylene glycol ester,
Cyclohexenyl group boric acid propylene glycol ester, cyclohexenyl group pinacol borate, cyclohexenyl group boric acid pinane diol ester,
Cyclo-octene base boronicacid ethylene glycol ester, cyclo-octene base boric acid propylene glycol ester, cyclo-octene base pinacol borate,
Cyclo-octene base boric acid pinane diol ester, cyclonoene acid ethylene glycol ester, cyclonoene ylboronic acid propylene glycol ester,
Cyclonoene ylboronic acid pinacol ester, cyclonoene ylboronic acid pinane diol ester, cyclodecene acid ethylene glycol ester,
Cyclodecene ylboronic acid propylene glycol ester, cyclodecene ylboronic acid pinacol ester, cyclodecene ylboronic acid pinane diol ester,
Where are cyclododecene acid ethylene glycol ester, cyclododecene ylboronic acid propylene glycol ester, cyclododecene ylboronic acid frequency
Alcohol ester, cyclododecene ylboronic acid pinane diol ester, ENB acid ethylene glycol ester, norbornene
Boric acid propylene glycol ester, norbornene pinacol borate or ENB ylboronic acid pinane diol ester.
According to the preferred embodiment of the present invention, the boric acid or boric acid ester compound (b) are selected from substitution
Or unsubstituted cyclenes ylboronic acid, cyclohexene boric acid dialkyl ester or cyclohexenyl group boric acid alkylidene diester.
In method of the present invention, the silicone compounds (a) and the boric acid or borate
The reaction ratio of compound (b) is such that the hydrogen in the silicone compounds (a) with silicon atom bonding is former
The mol ratio of the alkenyl in sub and described boric acid or boric acid ester compound (b) is at least 0.8, preferably
0.80-1.0, more preferably 0.80-0.95.
In method of the present invention, the silicon hydrogenation preferably enters in the presence of platinum group catalyst
OK.The example of the platinum group catalyst includes but is not limited to platinum black, platinum chloride, chloroplatinic acid, chloroplatinic acid
The reactant of alcoholic solution, chloroplatinic acid and alcohol, the reactant of chloroplatinic acid and olefin(e) compound, chloroplatinic acid with contain
The complex compound of the reactant, platinum-alkene complex or platinum-siloxanes containing vinyl of the siloxanes of vinyl.
Preferably, the platinum group catalyst is selected from the complex compound of platinum-siloxanes containing vinyl, such as platinum (0) -1,3-
Divinyl -1,1,3,3- tetramethyl disiloxane complex compounds.The consumption of the platinum alkene catalyst is relative to institute
The gross weight for stating silicone compounds (a) and the boric acid or boric acid ester compound (b) is usually
0.05-10000ppm, preferably 0.1-8000ppm, more preferably 0.5-5000ppm.
In method of the present invention, the silicon hydrogenation can be carried out under condition of no solvent,
Can carry out in a solvent.When the silicon hydrogenation is carried out in a solvent, the example bag of the solvent
Include but be not limited to：Fat hydrocarbon solvent, such as hexane, decane, dodecane；Aromatic hydrocarbon solvent, such as benzene,
Toluene, dimethylbenzene etc.；Halogenated hydrocarbon solvent, such as carbon tetrachloride, chloroform, dichloromethane, a chlorine
Methane etc.；Alcohols solvent, such as methyl alcohol, ethanol, isopropanol, n-butanol；Ether solvent, such as tetrahydrochysene
Furans, diethyl ether, butyl oxide etc.；Ketones solvent, such as acetone, MEK；Esters solvent, such as second
Acetoacetic ester, butyl acetate；Amide solvent, such as DMF, N, N- dimethylacetamides
Amine etc..The consumption of the solvent has no particular limits, and can be carried out according to actual conditions specifically chosen.
In method of the present invention, the temperature of the silicon hydrogenation is usually 50-150 DEG C, preferably
It is 60-100 DEG C.
In method of the present invention, the time of the silicon hydrogenation has no particular limits.Generally,
Determine reaction end by carrying out ftir analysis (FT-IR) to reactant mixture.
Specifically, when the signal peak disappearance in FT-IR display reactant mixtures with the hydrogen atom of silicon atom bonding
When, it is defined as reaction end.
In method of the present invention, after the silicon hydrogenation terminates, preferred pair reaction mixing
Thing carries out vacuum distillation.The effect of the vacuum distillation is to remove unreacted boric acid or borate chemical combination
Thing (b), organic solvent (if present) and other low-boiling-point substances.
<The purposes of boracic organo-silicon compound>
Boracic organo-silicon compound of the present invention have as addition curable organopolysiloxane group
The purposes of the tackifier of compound.It is organic that boracic organo-silicon compound of the present invention are used as addition curable
During the tackifier of polysiloxane composition, can be in hot and humid and UV environment for its solidfied material is carried
For cohesive stable sufficiently and for a long time.
In purposes of the present invention, the addition curable organopolysiloxane composition is generally comprised
At least one organopolysiloxane containing with the alkenyl of silicon atom bonding, at least one contain and silicon atom
The organic hydrogen polysiloxanes and silicon hydrogenation catalyst of the hydrogen atom of bonding.For organopolysiloxane,
The type and its consumption of the organic hydrogen polysiloxanes and the silicon hydrogenation catalyst are without special
Limitation, can use type well known in the art and consumption.
The example of the addition curable organopolysiloxane composition include but is not limited to by
CN102892837A、CN104395406A、CN104870568A、CN103154144A、
CN101443400A、CN102977604A、CN102276989A、CN104204100A、
Addition curable organopolysiloxane composition disclosed in CN102686598B.
In purposes of the present invention, relative to containing in addition curable organopolysiloxane composition
With the organopolysiloxane of the alkenyl of silicon atom bonding and containing organic with the hydrogen atom of silicon atom bonding
The weight portion of total consumption 100 of hydrogen polysiloxanes, as the boracic organo-silicon compound of tackifier
Consumption is preferably 0.5-20 weight portions, more preferably 1-10 weight portions.
Embodiment
The present invention is further described with reference to embodiment, application examples and contrast application examples, but
Protection scope of the present invention is not limited to this.
Synthesis example 1
The preparation of silicone compounds 1：
During the 1L four-hole boiling flasks of agitator, thermometer, condenser and dropping funel be will be equipped with as ice bath,
Under agitation successively to added in flask 107.46g (0.80mol) 1,1,3,3- tetramethyl disiloxanes,
100g deionized waters and 10g concentration are the concentrated hydrochloric acid of 37.5wt%.Then, to being slowly added dropwise in flask
107.79g (0.5mol) 3- cyclohexenyl group trichlorosilanes.After completion of dropping, continue under agitation anti-
Answer 1 hour.By product stratification, and separate water outlet phase.Organic phase washing 3 to being collected into
It is secondary, it is then that 5wt% sodium bicarbonate aqueous solutions are washed 3 times with concentration, wash again afterwards 3 times.In water
Add sodium sulphate to be dried in organic phase after washing, and filter sodium sulphate after the drying.After the drying
0.4g MEHQs are added in organic phase, 137.24g product is obtained through vacuum distillation.Pass through
The analysis of carbon nuclear resonance spectrum (13C-NMR) and silicon nuclear resonance spectrum analysis (29Si-NMR), institute is confirmed
Stating product has chemical constitution (calling silicone compounds 1 in the following text) shown in formula (II-1).By height
Effect liquid phase chromatogram (HPLC) is analyzed, and the purity for determining the product is 99.3%.
Synthesis example 2
The preparation of silicone compounds 2：
During the 1L four-hole boiling flasks of agitator, thermometer, condenser and dropping funel be will be equipped with as ice bath,
Under agitation successively to added in flask 107.46g (0.80mol) 1,1,3,3- tetramethyl disiloxanes,
100g deionized waters and 10g concentration are the concentrated hydrochloric acid of 37.5wt%.Then, to being slowly added dropwise in flask
113.80g (0.5mol) 5- ENB base trichlorosilanes.After completion of dropping, continue under agitation
Reaction 1 hour.By product stratification, and separate water outlet phase.Organic phase washing to being collected into
3 times, be then that 5wt% sodium bicarbonate aqueous solutions are washed 3 times with concentration, is washed again afterwards 3 times.
Add sodium sulphate to be dried in organic phase after washing, and filter sodium sulphate after the drying.After the drying
Organic phase in add 0.4g MEHQs, obtain 136.95g product through vacuum distillation.It is logical
Cross carbon nuclear resonance spectrum analysis (13C-NMR) and silicon nuclear resonance spectrum analysis (29Si-NMR), confirm
The product has the chemical constitution (calling silicone compounds 2 in the following text) shown in formula (II-2).Pass through
High performance liquid chromatography (HPLC) is analyzed, and the purity for determining the product is 99.1%.
Embodiment 1
The preparation of boracic organo-silicon compound 1：
In the tetra- mouthfuls of burnings of 250ml equipped with agitator, thermometer, condenser, dropping funel and nitrogen conduit
In bottle, the air led in nitrogen displacement flask sequentially adds 35.38g (0.17mol) under agitation
The platinum of cyclohexene -1- ylboronic acids pinacol ester, 0.04g MEHQs and 14ml platinum contents about 2wt%
(0) -1,3- divinyl -1, the toluene solution of 1,3,3- tetramethyl disiloxane complex compound, opens after stirring
Begin to heat.When temperature rise is to 70 DEG C in flask, 16.74g (0.05mol) is slowly added dropwise under agitation
The silicone compounds 1 obtained by synthesis example 1.After completion of dropping, flask is kept internal temperature at 80 DEG C,
Continue to react under agitation.To reaction mixture sampling, ftir analysis are carried out
(FT-IR).When the signal peak disappearance in FT-IR display reactant mixtures with the hydrogen atom of silicon atom bonding
When, it is defined as reaction end.Vacuum distillation is carried out to reactant mixture, unreacted cyclohexene -1- is removed
Ylboronic acid pinacol ester and other low-boiling-point substances, obtain 38.23g product.By carbon nuclear resonance spectrum
Analysis (13C-NMR) and silicon nuclear resonance spectrum analysis (29Si-NMR), confirm that product has formula
(I-7) chemical constitution (calling boracic organo-silicon compound 1 in the following text) shown in.By high performance liquid chromatography
(HPLC) analyze, the purity for determining the product is 96.5%.
Embodiment 2
The preparation of boracic organo-silicon compound 2：
In the tetra- mouthfuls of burnings of 250ml equipped with agitator, thermometer, condenser, dropping funel and nitrogen conduit
In bottle, the air led in nitrogen displacement flask sequentially adds 35.38g (0.17mol) under agitation
The platinum of cyclohexene -1- ylboronic acids pinacol ester, 0.04g MEHQs and 14ml platinum contents about 2wt%
(0) -1,3- divinyl -1, the toluene solution of 1,3,3- tetramethyl disiloxane complex compound, opens after stirring
Begin to heat.When temperature rise is to 70 DEG C in flask, 17.31g (0.05mol) is slowly added dropwise under agitation
The silicone compounds 2 obtained by synthesis example 2.After completion of dropping, flask is kept internal temperature at 80 DEG C,
Continue to react under agitation.To reaction mixture sampling, ftir analysis are carried out
(FT-IR).When the signal peak disappearance in FT-IR display reactant mixtures with the hydrogen atom of silicon atom bonding
When, it is defined as reaction end.Vacuum distillation is carried out to reactant mixture, unreacted cyclohexene -1- is removed
Ylboronic acid pinacol ester and other low-boiling-point substances, obtain 38.23g product.By carbon nuclear resonance spectrum
Analysis (13C-NMR) and silicon nuclear resonance spectrum analysis (29Si-NMR), confirm that product has formula
(I-15) chemical constitution (calling boracic organo-silicon compound 2 in the following text) shown in.By high performance liquid chromatography
(HPLC) analyze, the purity for determining the product is 95.7%.
Application examples 1
The preparation of addition curable organopolysiloxane composition：
Following each components are mixed, the addition curable organopolysiloxane group of application examples 1 of the present invention is prepared
Compound：
The end of 70 weight portion two is by Me2ViSiO1/2Unit terminated dimethyl silicone polymer, it is at 23 DEG C
When viscosity be 5000mPas, wherein being 0.12wt% with the contents of ethylene of silicon atom bonding；
30 weight portions are by Me3SiO1/2Unit, Me2ViSiO1/2Unit and SiO4/2Unit is constituted, and
Me3SiO1/2Unit and Me2ViSiO1/2Unit and SiO4/2The mol ratio (M/Q) of unit is 1.0
MQ resins, wherein being 5.4wt% with the contents of ethylene of silicon atom bonding；
5 weight portion main chains are by MeHSiO2/2Unit and Me2SiO2/2Unit constitute, and two ends by
Me3SiO1/2Unit terminated methylhydrogenpolysi,oxane, its viscosity at 23 DEG C is 30mPas, its
In with the hydrogen atom content of silicon atom bonding be 1.45wt%；
The silica of platinum (0) -1,3- divinyl -1,1,3,3- tetramethyls two of 0.04 weight portion platinum content about 2wt%
The toluene solution of alkane complex compound；
0.001 weight portion 1- ethynylcyclohexanols；
2 weight portion tackifier, it is the boracic organo-silicon compound 1 as prepared by embodiment 1.
Cohesive evaluation in hot and humid and UV environment：
By determining addition curable organopolysiloxane composition its solidfied material hot and humid and ultraviolet
It is right to the bonding strength and cohesional failure rate of glass plate after being exposed 0 hour and 1000 hours in thread environment
Its cohesive is evaluated, and relevant evaluation result is recorded in table 1 below.
Wherein, the assay method of bonding strength and cohesional failure rate is as follows：By the organic poly- silicon of addition curable
Silicone compositions are clipped in two pieces of glass plates that width is 25mm with the bond area of 12.5mm × 25mm
Between, in pressure be 0.3Kg/cm2, temperature be 120 DEG C under conditions of be heating and curing 1 hour, thus make
Obtain sample.By sample temperature be 85 DEG C, relative humidity be 100% and fluorescent ultraviolet lamp (340nm)
Exposed respectively in the environment of exposure 0 hour and 1000 hours, it is then opposite with level with cupping machine
Direction tensile sample two ends, determine tensile strength (unit during fracture：MPa), it is thus strong to bonding
Degree is evaluated.Meanwhile, the plane of disruption to sample is evaluated, and is determined glass plate and is not occurred with solidfied material
There is the area for being broken (cohesional failure) in itself relative to disconnected in interface peel (interfacial failure) and solidfied material
The ratio (percentage) of the broken face gross area, i.e. cohesional failure rate (%).
Application examples 2
The preparation of addition curable organopolysiloxane composition：
The boracic as prepared by embodiment 2 except the tackifier in application examples 1 to be replaced with same amount
Outside organo-silicon compound 2, other components and its consumption are identical with application examples 1.The each component is mixed
Close, prepare the addition curable organopolysiloxane composition of application examples 2 of the present invention.
Cohesive evaluation in hot and humid and UV environment：
The method for evaluating adhesion property of application examples 2 is identical with application examples 1, and relevant evaluation result is recorded following
In table 1.
Contrast application examples 1
The preparation of addition curable organopolysiloxane composition：
The implementation by CN103739848A except the tackifier in application examples 1 to be replaced with same amount
(it is by γ-glycidyl ether oxygen propyl trimethoxy silicane, aminomethyl phenyl to tackifier prepared by example 1
Dimethoxysilane, trimethylborate, vinyl dimethylethoxysilane are prepared through hydrolysis-condensation reaction
Form) outward, other components and its consumption are identical with application examples 1.The each component is mixed, is prepared
Contrast the addition curable organopolysiloxane composition of application examples 1.
Cohesive evaluation in hot and humid and UV environment：
The method for evaluating adhesion property for contrasting application examples 1 is identical with application examples 1, and relevant evaluation result record exists
In table 1 below.
Contrast application examples 2
The preparation of addition curable organopolysiloxane composition：
Except by the tackifier in application examples 1 replace with same amount as disclosed in JP2000169482A
Following formula shown in tackifier outside, other components and its consumption are identical with application examples 1.By each group
Divide mixing, prepare the addition curable organopolysiloxane composition of contrast application examples 2.
Cohesive evaluation in hot and humid and UV environment：
The method for evaluating adhesion property for contrasting application examples 2 is identical with application examples 1, and relevant evaluation result record exists
In table 1 below.
Contrast application examples 3
The preparation of addition curable organopolysiloxane composition：
Except by the tackifier in application examples 1 replace with same amount as disclosed in US5614640A
Outside tackifier shown in following formula, other components and its consumption are identical with application examples 1.By each component
Mixing, prepares the addition curable organopolysiloxane composition of contrast application examples 3.
Cohesive evaluation in hot and humid and UV environment：
The method for evaluating adhesion property for contrasting application examples 3 is identical with application examples 1, and relevant evaluation result record exists
In table 1 below.
Contrast application examples 4
The preparation of addition curable organopolysiloxane composition：
In addition to being added without any tackifier, other components and its consumption are identical with application examples 1.By institute
Each component mixing is stated, the addition curable organopolysiloxane composition of contrast application examples 4 is prepared.
Cohesive evaluation in hot and humid and UV environment：
The method for evaluating adhesion property for contrasting application examples 4 is identical with application examples 1, and relevant evaluation result record exists
In table 1 below.
Table 1
Can be seen that application examples 1-2's with the comparing of contrast application examples 1-4 by application examples 1-2 of the present invention
Addition curable organopolysiloxane composition is respectively with the boracic organosilicon compound of embodiment of the present invention 1-2
Thing as tackifier, its solidfied material temperature be 85 DEG C, relative humidity be 100% and fluorescent ultraviolet lamp
Exposure remains to keep at least bonding strength of 5.6MPa after 1000 hours in the environment of (340nm) exposure
At least 90% cohesional failure rate, that is, boracic organo-silicon compound of the present invention can be in height
Filled for the solidfied material of addition curable organopolysiloxane composition is provided in warm high humidity and UV environment
Divide and cohesive steady in a long-term.Additionally, the present invention prepares boracic organosilicon compound by silicon hydrogenation
Thing, is obtained in that chemical constitution is controllable, there is no accessory substance, and the boracic of quality and stable performance has
Organic silicon compound.
The present invention is not limited to above-mentioned implementation method, in the case of without departing substantially from substance of the invention,
It may occur to persons skilled in the art that any deformation, improvement, replacement each fall within the scope of the present invention.
Claims (9)
1. boracic organo-silicon compound, it is characterised in that it has the chemical constitution shown in formula (I)：
In formula (I)：
B is boron atom,
Q is the cycloalkenyl group of substituted or unsubstituted carbon number 3-20,
L is the cycloalkyl of substituted or unsubstituted carbon number 3-20,
Two OR being connected with B1In two R1The respectively alkyl of hydrogen atom or carbon number 1-20,
Or, two OR being connected with B1In two R1It is interconnected to form the alkylene of carbon number 2-20
Base.
2. boracic organo-silicon compound according to claim 1, it is characterised in that the Q choosings
From substituted or unsubstituted cyclopropanyl, cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclo-octene base,
Cyclonoene base, cyclodecene base, cyclododecene base or norbornene.
3. boracic organo-silicon compound according to claim 2, it is characterised in that the Q choosings
From substituted or unsubstituted cyclohexenyl group or norbornene.
4. boracic organo-silicon compound according to claim 1, it is characterised in that the L choosings
From substituted or unsubstituted cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl, cyclononyl, ring
Decyl, cyclo-dodecyl or norborneol alkyl.
5. boracic organo-silicon compound according to claim 4, it is characterised in that the L choosings
From substituted or unsubstituted cyclohexyl.
6. the method for preparing the boracic organo-silicon compound any one of claim 1-5, it is special
Levy and be, including：Make following material that silicon hydrogenation to occur：
Silicone compounds shown in (a) formula (II)：
In formula (II), Q is identical with defined in claim 1 formula (I),
Boric acid or boric acid ester compound shown in (b) formula (III)：
In formula (III)：
L ' is selected from the cycloalkenyl group of substituted or unsubstituted carbon number 3-20,
R1It is identical with defined in claim 1 formula (I).
7. method according to claim 6, it is characterised in that the L ' is selected from substitution or does not take
The cyclopropanyl in generation, cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclo-octene base, cyclonoene base, ring
Decene base, cyclododecene base or norbornene.
8. method according to claim 7, it is characterised in that the L ' is selected from substitution or does not take
The cyclohexenyl group in generation.
9. boracic organo-silicon compound according to any one of claim 1-5 will by right
Seek the purposes of boracic organo-silicon compound prepared by the method any one of 6-8, it is characterised in that
Its tackifier for being used as addition curable organopolysiloxane composition.
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| PCT/CN2016/095850 WO2017096945A1 (en) | 2015-12-07 | 2016-08-18 | Organic silicon compound containing boron, sealant for solar cell assembly and solar cell assembly |
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| CN111154453A (en) * | 2020-01-19 | 2020-05-15 | 厦门艾贝森电子有限公司 | Heat-resistant single-component addition type organic silicon adhesive and preparation method thereof |
| CN111183185A (en) * | 2017-10-10 | 2020-05-19 | 纳米及先进材料研发院有限公司 | Impact protection material and method for manufacturing same |
| CN111394054A (en) * | 2020-03-24 | 2020-07-10 | 新安天玉有机硅有限公司 | Silicone rubber for self-adhesive tape and preparation method thereof |
| WO2023116494A1 (en) * | 2021-12-20 | 2023-06-29 | 华为技术有限公司 | Adhesive composition and preparation method therefor, and optical adhesive film and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111183185A (en) * | 2017-10-10 | 2020-05-19 | 纳米及先进材料研发院有限公司 | Impact protection material and method for manufacturing same |
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| CN111154453A (en) * | 2020-01-19 | 2020-05-15 | 厦门艾贝森电子有限公司 | Heat-resistant single-component addition type organic silicon adhesive and preparation method thereof |
| CN111394054A (en) * | 2020-03-24 | 2020-07-10 | 新安天玉有机硅有限公司 | Silicone rubber for self-adhesive tape and preparation method thereof |
| WO2023116494A1 (en) * | 2021-12-20 | 2023-06-29 | 华为技术有限公司 | Adhesive composition and preparation method therefor, and optical adhesive film and use thereof |
| CN117126605A (en) * | 2023-10-27 | 2023-11-28 | 山东福瑞斯新材料科技有限公司 | Antistatic organosilicon paint and preparation method thereof |
| CN117126605B (en) * | 2023-10-27 | 2023-12-29 | 山东福瑞斯新材料科技有限公司 | Antistatic organosilicon paint and preparation method thereof |
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